CN1230983A - Detergent composition and its preparation - Google Patents
Detergent composition and its preparation Download PDFInfo
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- CN1230983A CN1230983A CN 97198105 CN97198105A CN1230983A CN 1230983 A CN1230983 A CN 1230983A CN 97198105 CN97198105 CN 97198105 CN 97198105 A CN97198105 A CN 97198105A CN 1230983 A CN1230983 A CN 1230983A
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/042—Acids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions
- C11D11/0082—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0065—Solid detergents containing builders
- C11D17/0073—Tablets
- C11D17/0086—Laundry tablets
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/046—Salts
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2082—Polycarboxylic acids-salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy carboxylic acids-salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38609—Protease or amylase in solid compositions only
Abstract
A process for making a detergent composition comprising: i) admixing a detergent surfactant and an acid source to form a surfactant/acid mixture; and ii) forming an agglomerated surfactant/acid mix.
Description
Technical field
The present invention relates to preparing washing agent method for compositions and be suitable for doing washing and the detergent composition of dishwashing method.
Background of invention
In granulated detergent available on the market, exist to the trend of higher bulk density with granular detergent composition development with higher detergent active ingredients content.Such washing composition provides bigger convenience to the human consumer and has reduced the amount of the wrapping material that finally will dispose simultaneously.
Much the prior aries of attempting in this direction have run into because the problem of the solubleness of the difference that low dissolution rate or formation gel produce.In general washing methods, consequently product draws the distribution box or the dosing unit of putting together with clothing in washing machine bad from the distribution of washing machine.The distribution of this difference usually is that the gelation when being contacted with water by high-load surfactant granules causes.This gel overslaugh part detergent powder is dissolved in the washing water, and this has reduced the effectiveness of this powder.This is the specific question under low hydraulic pressure and/or the low wash temperature.
In addition, also exist the trend that another trend promptly reduces or do not use phosphate builders recently, phosphate builders uses zeolite (silicon metal aluminic acid) to replace usually.Have been found that to contain zeolite builders poorer than the distribution of phosphorous hydrochlorate washing assistant.
EP-A-0578871 has described the method for the high bulk density detergent composition of attempting to prepare quick dissolving and effectively distributing.This method comprises particle diameter formulated together at the basic powder and the additional filler component of 150-1700 micron, because the filler particles of at least 20% (weight) is lower than 150 microns.This filler particles comprises Citrate trianion, phosphoric acid salt, carbonic acid (hydrogen) salt and silicate.
WO95/14767 relates to the non-spray-dried detergent powder of high-density of distributivity difference, and discloses and use Rosin Rammler particle diameter less than 800 microns Citrate trianion.
WO94/28098 discloses non-spray-dried detergent powder, and it contains ethoxylation uncle C8-18 alcohol, the composition of alkali metal aluminosilicate washing assistant and 5-40% (weight) water-soluble citrate.
EP-A-0639637 discloses with alkali metal percarbonate and has replaced perborate bleach so that improve the distribution and the dissolution rate of washing composition.The mixture of Citrate trianion or Citrate trianion and vitriol or carbonate can be used to apply this percarbonate bleach.In this respect, EP-A-0639639 also has similarly open.
Improve other method of distributing and comprise the foaming system of using.If washing composition contains the foaming system, so the gas of Chan Shenging for example carbonic acid gas impel detergent particles separately and prevent gelation.
The dispersiveness that utilizing bubbles improves granulated material has been widely used for pharmaceutical preparation and has suffered.In this respect, the most widely used foaming system combination that is citric acid and supercarbonate.The dispersiveness of utilizing this simple foaming system to improve the pesticide composition of the aquatic insect of control has been described, for example GB-A-2184946.
US-A-4414130 discloses the lotion-aid particle that uses easy decomposition with the zeolite based washing composition.Also disclose the use foaming material and dissolved and dissolve so that improve this particulate.Yellow soda ash or sodium bicarbonate can make up with this zeolite builders mixture, and the remainder of this washing composition can comprise: citric acid, sulfuric acid list sodium, boric acid or other suitable acidifying material, preferably use the encapsulated or agglomeration of supercarbonate, be used for producing carbonic acid gas with its reaction.
WO92/18596 discloses by with 2: 1-15: 1 specified weight can be realized the improved solubility/dispersibility of granulated detergent than mixture of sodium carbonate and citric acid.
EP-A-0534525 discloses and has used the citric acid with 350-1500 micron specified particle diameter.
US-A-5114647 discloses the health method for compositions of preparation compressed format, it comprises: a) alkaline carbonate is mixed forming acidic mixture with the solid, water soluble aliphatic carboxylic acid, b) suppress the acidic mixture that this acidic mixture prepares compressed format, c) the crush acidic mixture of this compressed format forms the particle of acidic mixture and d) this acidic mixed composition granule is mixed formation health composition with basic metal chloro isocyanurate and alkali metal hydrocarbonate.The problem of this method is the composition that may not necessarily obtain the identical particle component.
Adding citric acid causes alkalescence to reduce.Alkaline pH promotes to clean, removes stain and dirt suspension, therefore is necessary to make used citric acid content minimum.In addition, citric acid also is relatively costly component, and this has further strengthened citric acid is remained on the very necessity of low levels.We have made us unexpectedly finding: the invention provides preparing washing agent method for compositions, be used for composition satisfactorily thereby this method can reduce this sour content.We recognize this intimate mixture that needs detergent composition and this acid source in a particle, and we have invented the unexpected method that realizes this point.More particularly, the present invention can make the acid content in the detergent composition minimize, and also keeps its benefit as dispersing auxiliary simultaneously.
The document that all are quoted in the present specification relevant portion, all incorporated by reference in this article.
Summary of the invention
According to an aspect of the present invention, provide preparing washing agent method for compositions, it comprises i) thus cleaning composition tensio-active agent and acid source form the surfactant/acid mixture; Ii) form agglomerant surfactant/acid mixture.
According to another aspect of the present invention, provide a kind of detergent composition, said composition comprises granular basic composition, and it contains the mixture of detergent surfactant and acid source.
Therefore, the present invention relates to the intimate mixture of a kind of tensio-active agent and acid source, and its preparation method.
This detergent composition preferably also contains alkali source, and it can form this granular basic composition of part, so that mix with detergent surfactant and acid source in the inventive method, perhaps it can be used as isolating component adding.
We have found that: acid source of the present invention and alkali source are joined improved solvability and/or the dispersiveness of washing composition in laundry solution in the detergent composition, and eliminate or reduced the solid detergent particle and remain in the washing machine neutralization and be washed problem on the clothes.We think that thereby acid promptly discharges gas with alkali reaction in washings.This helps dispensing of detergent and makes insoluble of formation to reduce to minimum.
Detailed Description Of The Invention
The present invention includes detergent composition.Such composition comprises basic composition, and it contains one or more tensio-active agents, acid source and preferably contain the washing assistant material.Can prepare this basic composition by agglomeration.This basic composition can also contain alkali source.In addition, the component that this alkali source also can be used as separately joins in the basic composition of washing composition, and it is particle form preferably.The amount that this alkali source exists preferably this particle weight about 5% or lower.
This tensio-active agent is negatively charged ion or nonionogenic tenside preferably.Anion surfactant is particularly preferred.The amount that this tensio-active agent exists in the particle basic material preferably this particle weight at least about 15%.This acid source is organic acid preferably, or derivatives thereof, and the amount of its existence about 5-60% of this particle weight preferably.Said composition preferably also contains washing assistant, and it is the part of this basic composition preferably, and the amount of its existence is about 20-80% of this particle weight.This washing assistant is zeolite preferably.The optional components that can have other, and it adds with about 10% or lower amount of particle weight separately.
The fundamental sum optional components of detailed hereafter detergent composition and prepare the method for this washing composition.
The A detergent surfactant
The amount that this component exists is the 1-90% of detergent composition weight preferably, preferred 3-70%, more preferably 5-40%, more preferably 10-30%, most preferably 12-25%.Washing composition is preferably selected from negatively charged ion, nonionic, zwitter-ion, both sexes, cats product and its mixture.This tensio-active agent is negatively charged ion, nonionogenic tenside or its mixture preferably.When composition contains more than a kind of tensio-active agent, the 0.1-50% of the total surfactant weight that the amount that this additional surfactant exists preferably exists, more preferably 1-40%, most preferably 5-30%.When it exists, both sexes and zwitterionics common and one or more negatively charged ion and/or nonionic surfactant combinations use.
Anion surfactant
Surfactant system can comprise anion surfactant.Basically it all is suitable being used to wash any anion surfactant of purpose.These tensio-active agents comprise anion sulfate, sulfonate, carboxylate salt and sarkosine tensio-active agent salt (comprise, for example, sodium, potassium, ammonium and replacement ammonium be for example single, two and triethanolamine salt).The anion sulfate acid salt surfactant is preferred.
Other anion surfactant comprises: fatty acid amide, alkyl succinate and the sulfosuccinate of isethionate such as acyl isethinate, N-acyl taurine salt, methyl tauride, the monoesters of sulfo-succinic acid (particularly saturated or unsaturated C
12-C
18Monoesters) and the diester of sulfo-succinic acid (particularly saturated or unsaturated C
6-C
14Diester), acyl sarcosinate.Resinous acid and hydrogenant resinous acid also are suitable, for example sylvic acid, hydroabietic acid and resinous acid and the hydrogenated resin acid that is present in or is derived from fatty oil.
The anion sulfate acid salt surfactant
Be applicable to that anion sulfate tensio-active agent herein comprises: the uncle of straight or branched or secondary alkyl sulfate, alkyl ethoxy sulfate, fatty oil acylglycerol vitriol, alkyl phenol epoxy ethane ether salt, C
5-C
17Acyl group-N-(C
1-C
4Alkyl) and-N-(C
1-C
4Hydroxyalkyl) vitriol of glucosamine sulfate and the alkyl polysaccharide vitriol of alkyl polyglucoside (compound of described herein nonionic non-sulfuric acidization) for example.
Alkyl sulfate surfactant is preferably selected from the uncle C of straight chain and side chain
10-C
18Alkyl-sulphate, more preferably side chain C
11-C
15Alkyl-sulphate and straight chain C
12-C
14Alkyl-sulphate.
Alkyl ethoxy sulfate surfactant is preferably selected from the C of per molecule with the ethoxylation of 0.5-20 moles of ethylene oxide
10-C
18Alkyl-sulphate.More preferably, this alkyl ethoxy sulfate surfactant is a per molecule 0.5-7 mole, the C of preferred 1-5 oxyethane ethoxylation
11-C
18, C most preferably
11-C
15Alkyl-sulphate.
The present invention uses particularly preferred aspect the mixture of preferred alkyl-sulphate and alkyl ethoxy sulfate surfactant.Such mixture is disclosed among the PCT patent application WO93/18124.
The anion sulfoacid salt surfactant
Be applicable to that anionic sulphonate tensio-active agent herein comprises: C
5-C
20Linear alkylbenzene sulfonate, alkyl ester sulfonate, C
6-C
22Uncle or secondary paraffin sulfonate, C
6-C
24Alkene sulfonate, sulfonated multi-carboxylate, alkyl glycerol sulfonate, fatty acyl group glycerol sulfonate, fatty oil acylglycerol sulfonate and its any mixture.
The anionic carboxylic acid salt surfactant
Suitable anionic carboxylate tensio-active agent comprises: alkyl ethoxy carboxylate, alkyl polyethoxye multi-carboxylate's tensio-active agent and soap (" alkyl carboxyl "), particularly specific as described herein secondary soap.
Suitable alkyl ethoxy carboxylate comprises formula RO (CH
2CH
2O)
xCH
2COO
-M
+Those, wherein R is C
6-C
18Alkyl, x be in the scope of 0-10, this oxyethyl group be causing of distributing like this it is measured less than 20% when x is 0 by weight, M is a positively charged ion.Suitable alkyl polyethoxye multi-carboxylate tensio-active agent comprises formula RO-(CHR
1CHR
2-O)-R
3Those, wherein R is C
6-C
18Alkyl, x are 1-25, R
1And R
2Be selected from hydrogen, methyl acid group, succsinic acid group, hydroxy succinic acid group and its mixture, R
3Be selected from alkyl and its mixture of hydrogen, replacement or the unsubstituted 1-8 of a having carbon atom.
Suitable soap surfactant comprises that containing the carboxyl unit is connected to secondary soap surfactant on the secondary carbon(atom).The preferred secondary soap surfactant that is used for herein is water miscible, and it is selected from 2-methyl isophthalic acid-undecanoic acid, 2-ethyl-1-capric acid, 2-propyl group-1-n-nonanoic acid, 2-butyl-1-is sad and the water-soluble salt of 2-amyl group-1-enanthic acid.Also can comprise the soap that some is specific as suds suppressor.
The basic metal sarcosinate surfactant
Other suitable anion surfactant is formula R-CON (R
1) CH
2The basic metal sarcosinate of COOM, wherein R is C
5-C
17Straight or branched alkyl or alkenyl, R
1Be C
1-C
4Alkyl, M are alkalimetal ions.Preferred example is the myristyl and the oleoyl methyl sarcosinate of its sodium-salt form.
Oxyalkylated nonionogenic tenside
Basically any oxyalkylated nonionogenic tenside all is suitable for herein.Ethoxylation and propenoxylated nonionogenic tenside are preferred.
The nonionogenic tenside of preferred alkoxylated is selected from: the Fatty Alcohol(C12-C14 and C12-C18) of the nonionic condenses of alkylphenol, the alcohol of nonionic ethoxylation, nonionic ethoxylated/propoxylated, have the nonionic ethoxylate/propoxylated glycerine condenses of propylene glycol and have the nonionic ethoxylate condensation product of propylene oxide/quadrol affixture.
Nonionic alcohol alcoxylates tensio-active agent
The condensation product of fatty alcohol and 1-25 mole alkylene oxide, especially oxyethane and/or propylene oxide is applicable to herein.The alkyl chain of this fatty alcohol can be straight or branched, uncle or secondary, and contain 6-22 carbon atom usually.Particularly preferably be the alkyl alcohol with 8-20 carbon atom and the condensation product of every mol of alcohol 2-10 moles of ethylene oxide.
The nonionic polyhydroxy fatty acid amide surfactant
Be applicable to that polyhydroxy fatty acid amide herein is to have formula R
2CONR
1Those materials of Z, wherein: R
1Be H, C
1-4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl, oxyethyl group, propoxy-, or its mixture, preferred C
1-C
4Alkyl, more preferably C
1Or C
2Alkyl, most preferably C
1Alkyl (being methyl); R
2Be C
5-
31Alkyl, preferred straight chain C
5-C
19Alkyl or alkenyl, more preferably straight chain C
9-C
17Alkyl or alkenyl, most preferably straight chain C
11-C
17Alkyl or alkenyl, or its mixture; Z be have the straight-chain alkyl chain, at least 3 hydroxyls are directly connected to the polyhydroxy alkyl on this chain, or its oxyalkylated (preferred ethoxylation or propenoxylated) derivative.Z preferably in reductive amination process from the reducing sugar deutero-; More preferably Z is glycityl.
The nonionic fatty acid amide surfactant
The suitable fatty acids acidamide surfactant comprises having formula R
6CON (R
7)
2Those materials, R wherein
6Be to contain 7-21, the alkyl of preferred 9-17 carbon atom, each R7 is selected from hydrogen, C
1-C
4Alkyl, C
1-C
4Hydroxyalkyl and (C
2H
4O)
xH, wherein x is the integer of 1-3.
Nonionic alkyl polysaccharide tensio-active agent
Be used for the US4565647 that herein suitable alkyl polysaccharide is disclosed in the Llenado of promulgation on January 21st, 1986, it has the hydrophobic group that contains 6-30 carbon atom and contains 1.3-10 the unitary glycan of saccharides (for example glycan glycosides) hydrophilic radical.
Preferred alkyl poly glucoside has following formula:
R
2O (C
nH
2nO)
t(glycosyl)
x
R wherein
2Be selected from: alkyl, alkyl phenyl, hydroxyalkyl, hydroxyalkyl phenyl and its mixture, wherein alkyl contains 10-18 carbon atom; N is 2 or 3; T is 0-10; X is 1.3-8.This glycosyl is preferably from the glucose deutero-.
Amphoterics
The suitable amphoterics that is used for herein comprises amine oxide surfactant and alkyl both sexes carboxylic acid.
Suitable amine oxide comprises having formula R
3(OR
4)
xN
0(R
5)
2Those compounds, R wherein
3Be selected from the alkyl, hydroxyalkyl, acyl group amido propyl group and the alkyl phenyl that contain 8-26 carbon atom, or its mixture; R
4Be alkylidene group or the hydroxy alkylidene that contains 2-3 carbon atom, or its mixture; X is 0-5, preferred 0-3; Each R
5It is the polyethylene oxide base that contains the alkyl or the hydroxyalkyl of 1-3 carbon atom or contain 1-3 ethylene oxide group.C preferably
10-C
18Alkyl dimethyl amine oxide and C
10-C
18Acyl group amidoalkyl dimethyl oxidation amine.
The suitable example of alkyl apho dicarboxylic acid is by Miranol, Inc., Dayton, Miranol (TM) the C2M Conc that Nj. produces.
Zwitterionics
Also zwitterionics can be incorporated in this detergent composition.These tensio-active agents can briefly be described as the derivative of the second month in a season or tertiary amine, the derivative of the heterocyclic second month in a season or tertiary amine, or quaternary ammonium, season rattle or the derivative of uncle's sulfonium compound.Trimethyl-glycine and sultaine tensio-active agent are the examples that is used for zwitterionics herein.
Suitable sultaine is to have formula R (R
1)
2N
+R
2COO
-Those compounds, wherein R is C
6-C
18Alkyl, each R
1Generally be C
1-C
3Alkyl, R
2Be C
1-C
5Alkyl.Preferred trimethyl-glycine is C
12-18Ammonio hexanoate of dimethyl and C
10-18Acyl group amido propane (or ethane) dimethyl (or diethyl) trimethyl-glycine.The coordinate beet alkali surface activator also is applicable to herein.
Cats product
The detergent composition that also additional cats product can be used for this paper.Suitable cationic surfactants comprises quaternary surfactant, and it is selected from single C
6-C
16, preferred C
6-C
10N-alkyl or alkenyl ammonium surfactant, wherein remaining N position is replaced by methyl, hydroxyethyl or hydroxypropyl.
The cationic ester tensio-active agent
Surfactant system can comprise the cationic ester tensio-active agent.It preferably has surfactant properties and contains at least one ester (compound of the water dispersible of key and at least one positively charged ion charged group promptly-COO-).
For example, suitable cationic ester tensio-active agent (comprising the cholinesterase tensio-active agent) is at US4228042,4239660 and US4260529 in disclose.
The cationic ester tensio-active agent of preferred water dispersible is the cholinesterase with following formula:
R wherein
1Be C
11-C
19The straight or branched alkyl chain.
Particularly preferred this cholinomimetic ester comprises: stearyl-cholinesterase season ammonium methyl halogenide (R
1=C
17Alkyl), palmitoyl cholinesterase season ammonium methyl halogenide (R
1=C
15Alkyl), myristoyl cholinesterase season ammonium methyl halogenide (R
1=C
13Alkyl), lauroyl cholinesterase season ammonium methyl halogenide (R
1=C
11Alkyl), coconut acyl group cholinesterase season ammonium methyl halogenide (R
1=C
11-C
13Alkyl), tallow acyl group cholinesterase season ammonium methyl halogenide (R
1=C
15-C
17Alkyl) and its any mixture.
Aspect preferred, this cationic ester tensio-active agent is hydrolyzable under laundry washing methods condition.
The B acid source
According to the present invention, acid source is to exist like this in detergent composition, thereby makes it produce gas with the alkali source reaction.
The amount that this acid source exists preferably composition weight about 15%.Preferably be up to approximately 10%, more preferably be up to about 7% (weight).As mentioned above, its advantage is to use acid source as few as possible, we have found that: the present invention can use about 0.25-5% low content like that.In the preferred embodiment of the invention, the amount that acid source exists is about 1-3% of composition weight, most preferably from about 3%.
This acid source can be any suitable organic, mineral or mineral acid, or derivatives thereof, or its mixture.This acid source can be single, two or three protonic acids.Preferred derivative comprises the salt or the ester of acid.This acid source is preferably nonhygroscopic, so that improve stability in storage.The organic acid or derivatives thereof is preferred.This acid is preferably water miscible.Suitable acid comprises: citric acid, pentanedioic acid, succsinic acid or hexanodioic acid, mono phosphoric acid ester sodium, sodium pyrosulfate, boric acid, or its salt or ester.Citric acid is particularly preferred.
Other suitable acid source is known to those skilled in the art.
The alkali source that C is optional
According to the present invention, alkali source is to exist like this in detergent composition, thereby makes it produce gas with the acid source reaction.This gas is carbonic acid gas preferably, so this alkali is carbonate, or its suitable derivative.
Detergent composition of the present invention preferably contains the 2-75% that has an appointment, more preferably from about 5-60%, the most preferably from about alkali source of 10-30% (weight).When this alkali source was present in the agglomerant detergent particles, this agglomerate preferably contained this alkali source of the 10-60% that has an appointment.
In preferred embodiments, this alkali source is a carbonate.The example of preferred carbonate is alkaline-earth metal and alkaline carbonate, and any mixture that comprises yellow soda ash, sodium bicarbonate and sesquicarbonate and itself and calcium carbonate superfine powder is for example disclosed on November 15th, 1973 disclosed German patent application 2321001.Alkali metal percarbonate also is in the source of suitable carbonate material and " the inorganic perhydrate salt " that the is described in this paper in more detail joint.
Other suitable alkali source is known to those skilled in the art.
This alkali source can comprise other component, for example silicate.Suitable silicate comprises SiO
2: Na
2O is than being the water-soluble metasilicate of 1.0-2.8, and this is than being preferred for 1.6-2.0, and 2.0 ratio is most preferred.This silicate can be anhydrous salt or salt hydrate form.SiO
2: Na
2O is most preferred silicate than the water glass that is 2.0.The basic metal persilicate also is suitable herein silicate source.
The preferred crystalline layered silicate that is used for herein has general formula: NaMSi
xO
2x+1YH
2O, wherein M is sodium or hydrogen, and x is 1.9-4, and y is 0-20.This class crystalline layered silicate is disclosed among the EP-A-0164514, and its preparation method is disclosed among DE-A-3417649 and the DE-A-3742043.Here, the x above in the general formula preferably has 2,3 or 4 value and preferably 2.Most preferred material is the δ-Na that can obtain with NaSKS-6 from Hoechst AG
2Si
2O
5
Additional detergent component
Detergent composition of the present invention also can contain additional detergent component.The definite character of these annexing ingredients and the amount of its adding depend on the physical form of composition and use the definite character of its washing operation.
Composition of the present invention preferably contains one or more additional detergent components, and it is selected from additional surfactant, SYNTHETIC OPTICAL WHITNER, washing assistant, the compound of organic polymer, enzyme, suds suppressor, lime soap dispersing agent, dirt suspension and anti redeposition agent and corrosion inhibitor.
The water soluble detergency promoter compound
Detergent composition of the present invention preferably contains water miscible washing-aid compound, and its general amount is the 1-80% of composition weight, preferred 10-70%, most preferably 20-60%.
Suitable water soluble detergency promoter compound comprises: water miscible monomer multi-carboxylate or its sour form, the multi-carboxylate of homopolymerization or copolymerization or its salt, wherein this multi-carboxylate comprises at least 2 by no more than 2 carboxyls that carbon atom is separated from each other, borate, phosphonate and above-mentioned any mixture.
This carboxylate salt or multi-carboxy acid salt washing agent can be monomer or oligomeric type, but because cost and performance, monomeric multi-carboxylate is normally preferred.
The suitable carboxylate salt that contains 1 carboxyl comprises: the water-soluble salt of lactic acid, oxyacetic acid and its ether derivant.The multi-carboxylate of containing 2 carboxyls comprises: the water-soluble salt of succsinic acid, propanedioic acid, (ethylenedioxy) oxalic acid, toxilic acid, diethyl alkyd, tartrate, tartronic acid and fumaric acid, and ether carboxylate and sulfinyl carboxylate salt.The multi-carboxylate of containing 3 carboxyls comprises: particularly, water-soluble citrate, aconitate and citraconate and succinate derivative, for example, the carboxyl methoxy succinate described in the English Patent 1379241, the newborn oxidation succinate described in the English Patent 1389732 and at the aminosuccinic acid salt described in the Holland application 7205873 and oxygen multi-carboxylate material for example at the 2-oxa--1 described in the English Patent 1387447,1,3-tricarballylic acid salt.
The multi-carboxylate of containing 4 carboxyls comprises: disclosed oxygen di-succinate, 1,1,2 in English Patent 1261829,2-ethane tetracarboxylic acid hydrochlorate, 1,1,3,3-propane tetracarboxylic acid salt and 1,1,2,3-propane tetracarboxylic acid salt.Containing the substituent multi-carboxylate of sulfo group comprises: English Patent 1398421 and 1398422 and US3936448 in disclosed sulfo-succinic acid salt derivative and at the sulfonation pyrolytic Citrate trianion described in the English Patent 1439000.Preferred multi-carboxylate is that per molecule contains the hydroxycarboxylate who is up to 3 carboxyls, Citrate trianion more specifically.
The mixture of the parent acid of monomer or oligomeric multi-carboxylate's sequestrant or itself and their salt, for example citric acid or Citrate trianion/citric acid mixture also are considered to useful builder component.
The borate washing assistant and contain can washing composition store or wash conditions under produce boratory one-tenth borate material washing assistant also be useful water soluble detergency promoter in this article.
The suitable example of water-soluble phosphate washing assistant is an alkali metal tripolyphosphates, trisodium phosphate, potassium and ammonium, and sodium orthophosphate and potassium, the polymerization degree is at the Sodium polymetaphosphate of about 6-21 scope, and phytate.
Be partly dissolved or insoluble washing-aid compound
Detergent composition of the present invention can contain and is partly dissolved or insoluble washing-aid compound, and its amount generally is the 1-80% of composition weight, preferred 10-70%, most preferably 20-60%.
Basically the example of water-fast washing assistant comprises sodium silicoaluminate.Suitable aluminosilicate zeolite has structure cell formula Na
z[(AlO
2)
z(SiO
2)
y] xH
2O, wherein z and y are at least 6, and the mol ratio of z and y is 1.0-0.5, and x is 5 at least, preferred 7.5-276, more preferably 10-264.This alumino-silicate materials be hydrated form and crystalline preferably, contain 10-28%, more preferably the water of 18-22% combining form.
This aluminosilicate zeolite can be naturally occurring material, but preferably synthetic obtaining.Synthetic crystal aluminosilicate ion-exchange material can zeolite A, and the title of zeolite B, zeolite P, X zeolite, zeolite HS and its mixture obtains.Zeolite A has formula Na
12[(AlO
2)
12(SiO
2)
12] xH
2O, wherein x is 20-30, particularly about 27.X zeolite has formula Na
86[(AlO
2)
86(SiO
2)
106] 276H
2O.
The organic peroxide acid bleach system
A preferable feature of detergent composition of the present invention is the organic peroxide acid bleach system.In preferred embodiments, this bleach system contains hydrogen peroxide cource and organic peroxide acid bleach precursor compound.Reaction in by this precursor and hydrogen peroxide cource produces organic peroxide acid.Preferred hydrogen peroxide cource comprises inorganic perhydrate SYNTHETIC OPTICAL WHITNER.In another preferred embodiment, the ready-formed organic peroxide acid is directly joined in the composition.Also consider to use contain hydrogen peroxide cource and organic peroxy acid precursor and with the composition of the mixture of ready-formed organic peroxide acid combination.
Inorganic perhydrate SYNTHETIC OPTICAL WHITNER
Inorganic perhydrate salt is preferred hydrogen peroxide cource.These salt are usually with an alkali metal salt, and the form of particular certain cancers adds, and its content is the 1-40% of composition weight, preferred 2-30%, most preferably 5-25%.
The example of inorganic perhydrate salt comprises: perborate, percarbonate, superphosphate, persulphate and persilicate.This inorganic perhydrate salt is an alkali metal salt normally.This inorganic perhydrate salt can comprise as there not being the crystalline solid of protection in addition., for some perhydrate salt, the preferred embodiment of such particulate composition is used this material of the coated form that better perhydrate salt stability in storage is provided in particulate product.Suitable coating material comprises inorganic salt for example alkalimetal silicate, carbonate or borate, or its mixture, perhaps for example wax, oil or fatty soap of organic materials.
Sodium peroxoborate is preferred perhydrate salt and can is that chemical formula is NaBO
2H
2O
2Monohydrate or chemical formula be NaBO
2H
2O
23H
2The tetrahydrate of O.
Alkali metal percarbonate, particularly SPC-D are preferred herein perhydrate.SPC-D is to have corresponding to formula 2Na
2CO
33H
2O
2Addition compound, and can be used as crystalline solid and buy.
The peroxide Potassium peroxysulfate is another inorganic perhydrate salt that is used for this paper detergent composition.
Peroxyacid bleach precursor
Peroxyacid bleach precursor is the compound that forms peroxy acid in crossing hydrolysis reaction with hydroperoxidation.Usually peroxyacid bleach precursor can be expressed as:
Wherein L is a leavings group, and X is any functional group basically, causes the structure of the peroxy acid that produces when crossing hydrolysis to be:
By detergent composition weight, the peroxyacid bleach precursor compound is preferably with 0.5-20%, more preferably 1-15%, and most preferably the amount of 1.5-10% adds.
Suitable peroxyacid bleach precursor generally contains one or more N-or O-acyl group, and this precursor can be selected from all kinds.Suitable type comprises: the acyl derivative of acid anhydrides, ester, imide, lactan and imidazoles and oxime.Example of useful materials is disclosed among the GB-A-158789 in such.Suitable ester is disclosed among English Patent 836988,864798,1147871,2143231 and the EP-A-0170386.
Leavings group
Leavings group, L group hereinafter must its reactivity be enough in the time period (for example cycles of washing) in the best hydrolysis reaction take place., if the L reactivity is too strong, will be difficult to stablize for being used for this activator of bleaching composition so.
Preferred L group is selected from following these groups and its mixture:
With
With
R wherein
1Be alkyl, aryl or the alkaryl that contains 1-14 carbon atom, R
3Be the alkyl chain that contains 1-8 carbon atom, R
4Be hydrogen or R
3, Y is H or solubilizing group, any R
1, R
3And R
4Basically can be replaced by any functional group, these functional groups comprise: for example alkyl, hydroxyl, alkoxyl group, halogen, amine, nitrosyl radical, acid amides and ammonium or alkyl ammonium group.
Preferred solubilizing group is-SO
3 -M
+,-CO
2 -M
+,-SO
4 -M
+,-N
+(R
3)
4X
-And O＜--(R
3)
3, most preferably-SO
3 -M
+With-CO
2 -M
+, R wherein
3Be the alkyl chain that contains 1-4 carbon atom, M is the positively charged ion that solvability is offered this bleach-activating agent, and X is the negatively charged ion that solvability is offered this bleach-activating agent.Preferably, M is basic metal, ammonium or replacement ammonium cation, and sodium and potassium are most preferred, and X is halogen, oxyhydroxide, methylsulfate or acetate anion.
Alkyl percarboxylic acids bleach precursor
Alkyl percarboxylic acids bleach precursor forms percarboxylic acids when crossing hydrolysis.Preferred this class precursor provides peracetic acid when crossing hydrolysis.
The alkyl peroxycarboxylic acid precursors compound of preferred imide type comprises N-, N, N
1N
1The Alkylenediamine of tetra-acetylatedization, wherein this alkylidene group contains 1-6 carbon atom, and especially wherein this alkylidene group contains those compounds of 1,2 or 6 carbon atom.Tetra acetyl ethylene diamine (TAED) is particularly preferred.
Other preferred alkyl peroxycarboxylic acid precursors comprises: 3,5,5-trimethyl acetyl oxygen base benzene sulfonic acid sodium salt (different-NOBS), acyloxy benzene sulfonic acid sodium salt in the ninth of the ten Heavenly Stems (NOBS), acetoxyl group benzene sulfonic acid sodium salt (ABS) and penta-acetyl glucose.
The alkyl peroxy acids precursor that acid amides replaces
The alkyl peroxy acids precursor that acid amides replaces is suitable for herein, comprises those compounds with following general formula:
Or
R wherein
1Be alkyl with 1-14 carbon atom, R
2Be the alkylidene group that contains 1-14 carbon atom, R
5Be H or the alkyl that contains 1-10 carbon atom, L can be any leavings group basically.The bleach activating immunomodulator compounds that this class acid amides replaces is described among the EP-A-0170386.
Peroxybenzoic acid precursors
The peroxybenzoic acid precursors compound provides peroxybenzoic acid when crossing hydrolysis.The phenylformic acid precursor compound of suitable neighbour-acylations comprises and replacing or unsubstituted benzoyloxy benzene sulfonate; with the product with the formylated sorbyl alcohol of benzoyl reagent benzene, glucose and all saccharidess, these compounds of acid imide comprise the urea that N-benzoyl succinimide, four benzoyl quadrols and N-benzoyl replace.Suitable imidazoles peroxybenzoic acid precursors comprises N-benzoyl imidazoles and N-benzoyl benzo imidazoles.The peroxybenzoic acid precursors that contains the N-acyl group that other is useful comprises N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl Pyrrolidonecarboxylic acid.
The positively charged ion peroxyacid precursor
The positively charged ion peroxyacid precursor produces the positively charged ion peroxy acid when crossing hydrolysis.
Usually, the positively charged ion peroxyacid precursor is by with positively charged functional group for example ammonium or alkylammonium, and preferred ethyl or ammonium methyl replace that the peroxy acid of suitable peroxyacid precursor compound partly forms.The positively charged ion peroxyacid precursor general as with suitable negatively charged ion for example the salt of halide ions be present in the solid detergent composition.
The peroxyacid precursor compound of positively charged ion replacement can be the derivative of peroxybenzoic acid or its replacement, precursor compound as previously described like this.In addition, this peroxyacid precursor compound can be the alkyl peroxy acids precursor that alkyl peroxycarboxylic acid precursors compound or acid amides replace, and is as mentioned below.
The positively charged ion peroxyacid precursor is described in United States Patent (USP) 4904406,4751015,4988451,4397757,5269962,5127852,5093022,5106528; English Patent 1382594; European patent 475512,458396 and 284292; And among the Japanese Patent 87-318332.
The example of preferred cation peroxyacid precursor is described in UK Patent Application 9407944.9 and U.S. Patent application 08/29803,08/298650,08/298904 and 08/298906.
Suitable positively charged ion peroxyacid precursor comprises alkyl or the tetra-acetylated glucose benzoyl peroxide of benzoyl oxygen benzene sulfonate, N-acylations hexanolactam and single benzoyl that ammonium or alkylammonium replace.Preferred N-acylations hexanolactam cationoid peroxyacid precursor comprises trialkyl ammonium methylene radical benzoyl caprolactam and trialkyl ammonium methylene radical alkyl hexanolactam.
Benzoxazine organic peroxy acid precursor
Also suitable is benzoxazine peroxide acids precursor compound, as disclosed in EP-A-332294 and EP-A-482807, particularly has those compounds of following formula:
R wherein
1Be H, alkyl, alkaryl, aryl or arylalkyl.
Preformed organic peroxide acid
Except the organic peroxide acid bleach precursor, perhaps as the quid pro quo of organic peroxide acid bleach precursor, this organic peroxide acid bleach system can contain preformed organic peroxide acid, and with composition weight meter, its amount is generally 1-15%, more preferably 1-10%.
The compound that the acid amides that a preferred class organic peroxy acid compound is following general formula replaces:
Or
R wherein
1Be alkyl, aryl or alkaryl with 1-14 carbon atom, R
2Be alkylidene group, arylidene and the alkyl arylene that contains 1-14 carbon atom, R
5Be H or alkyl, aryl or the alkaryl that contains 1-10 carbon atom.The organic peroxy acid compound that this class acid amides replaces is described among the EP-A-0170386.
Other organic peroxide acid comprises diacyl and four acyl peroxides, especially diperoxy dodecanedioic acid, diperoxy tetradecane diacid and diperoxy Thapsic acid.List and two is crossed nonane diacid, undecane dicarboxylic acid crossed by list and two and the amino peroxide hexanodioic acid of N-phthaloyl also is suitable for herein.
Bleaching catalyst
Composition randomly contains the bleaching catalyst of transition metal.The bleaching catalyst that one class is suitable is to contain to limit the active heavy metal cation of bleach catalyst for example copper, iron or manganese positively charged ion, with have very little or do not have the active assistant metal positively charged ion of bleach catalyst for example zinc or aluminium cations, and catalysis and assistant metal positively charged ion had a catalyst system of sequestrant, the especially ethylenediamine tetraacetic acid (EDTA), ethylenediamine tetraacetic (methylene phosphonic acid) and its water-soluble salt that limit stability constant.Such catalyzer is disclosed among the US4430243.
The bleaching catalyst of other type comprises disclosed manganese basigamy compound among US5246621 and the US5244594.The preferred example of this class catalyzer comprises: Mn
IV 2(u-O
)3 (1,4,7-trimethylammonium-1,4,7-7-triazacyclononane)
2-(PF
6)
2, Mn
III 2(u-O)
1(u-OAc)
2(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) 2-(PF
6)
2, Mn
III 2(u-O)
1(u-OAc)
2(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane)
2-(ClO
4)
2, Mn
IV 4(u-O)
6(1,4, the 7-7-triazacyclononane)
4-(ClO
4)
2, Mn
IIIMn
IV 4(u-O)
1(u-OAc)
2-(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane)
2-(ClO
4)
3With its mixture.Being described in the european patent application 549272 of other.Be applicable to that other ligand herein comprises: 1,5,9-trimethylammonium-1,5,9-7-triazacyclononane, 2-methyl isophthalic acid, 4,7-7-triazacyclononane, 2-methyl isophthalic acid, 4,7-7-triazacyclononane, 1,2,4,7-tetramethyl--1,4,7-7-triazacyclononane and its mixture.
The example of suitable bleaching catalyst is seen US4246612 and US5227084.Referring to US5194416, it discloses for example Mn (1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) (OCH of monokaryon manganese (IV) complex compound
3)
3(PF
6).Another kind of bleaching catalyst, disclosed as US5114606, be manganese (III) and/or (IV) with the water soluble complex of non-carboxylate salt polyol ligand with at least 3 C-OH groups of connecting.Other example comprises and the double-core Mn of the complexing of four-N-dentate and two-N-dentate ligand, comprises N
4Mn
III 3(u-O)
2Mn
IVN
4)
+[bipy
2Mn
III(u-O)
2Mn
IVBipy
2]-(ClO
4)
3
Other suitable bleaching catalyst is described in, for example european patent application 408131 (cobalt complex catalyst), European patent application publication No. 384503 and 306089 (catalysis of metalloporphyrin agent), US4728455 (manganese/polygamy position polymerization of olefin using catalyst body catalyst), US4711748 and European patent application publication No. 224952 (manganese is adsorbed on catalyzer on the silico-aluminate), US4601845 (aluminosilicate carrier) with manganese and zinc or magnesium salts, US4626373 (manganese/ligand catalyzer), US4119557 (nominal price iron complex catalyzer), German Patent 2054019 (cobalt sequestrant catalyzer), Canadian patent application 866191 (containing transition metal salt), US4430243 (sequestrant) and US4728455 (manganese gluconate catalyzer) with manganese positively charged ion and on-catalytic metallic cation.
Heavy metal ion chelating agent
Detergent composition of the present invention preferably contains the heavy metal ion chelating agent as optional components.Referred to the component of sequester heavy metal ion effect herein about " heavy metal ion chelating agent ".These components also can have calcium and magnesium sequestering power, but preferably they demonstrate for example selectivity of iron, manganese and copper of bonding heavy metal.
In the weight of composition, heavy metal ion chelating agent is usually with 0.005-20%, preferred 0.1-10%, and more preferably 0.25-7.5%, most preferably the amount of 0.5-5% exists.
The suitable heavy metal ion chelating agent that is used for herein comprises: organic phosphonate is poly-(alkylene phosphonic acids salt), basic metal ethane 1-hydroxyl diphosphonate of amino alkylidenyl, nitrilo trimethylene phosphonic salt for example.
Preferably diethylenetriamine five (methylene phosphonic acid salt), ethylene diamine three (methylene phosphonic acid salt), hexamethylene-diamine four (methylene phosphonic acid salt) and hydroxy ethylene 1,1 diphosphonate in the above-mentioned substance.
Other the suitable heavy metal ion chelating agent that is used for herein comprises: nitrilotriacetic acid(NTA) and polyaminocarboxylic acid be the amino tetraacethyl of ethylene, ethylidene pentaacetic acid, ethylenediamine disuccinic acid, quadrol two pentanedioic acids, 2-hydroxypropyl diamines disuccinic acid or its any salt for example.Particularly preferably be quadrol-N, N '-disuccinic acid (EDDS) or its basic metal, alkaline-earth metal, ammonium or substituted ammonium salt, or its mixture.
The iminodiacetic acid derivatives that is used for herein other suitable heavy metal ion chelating agent and is being described in EP-A-317542 and EP-A-399133 is 2-hydroxyethyl oxalic acid or glyceryl iminodiethanoic acid for example.Iminodiethanoic acid-N-2-hydroxypropyl the sulfonic acid and the aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrant that are described among the EP-A-516102 also are suitable for herein.Be described in the Beta-alanine-N among the EP-A-509382, N '-oxalic acid, aspartic acid-N, single acetate of N '-oxalic acid, aspartic acid-N-and imino-diacetic succsinic acid sequestrant also are suitable.
EP-A-476257 has described the sequestrant of suitable amino based.EP-A-510331 has described from collagen protein, Keratin sulfate or casein derived suitable sequestrant.EP-A-528859 has described suitable alkyl imino oxalic acid sequestrant.Two pyridine carboxylic acids and 2-phosphorus butane-1,2, the 4-tricarboxylic acid also is suitable.G-NH2-N, N '-disuccinic acid (GADS), quadrol-N, N '-two pentanedioic acid (EDDG) and 2-hydroxyl propylene diamine-N, N '-disuccinic acid (HPDDS) also is suitable.
Enzyme
Another preferred ingredient useful in detergent composition is one or more additional enzymes.
Preferred additional enzyme material comprises lipase, at, amylase, neutrality and Sumizyme MP, esterase, cellulase, polygalacturonase, Sumylact L and the peroxidase of buying on the market that is routinely added in the detergent composition.Suitable enzyme is disclosed among US3519570 and the US3533139.
The proteolytic enzyme that preferred commerce is buied comprises: those that sold with trade name Alcalase, Savinase, Primase, Durazym and Esperase by Novo Industries A/S (Denmark), those that sell with trade name Maxatase, Maxacal and Maxapem by Gist-Brocades, those that sell by Genencor International and sell with trade name Opticlean and Optimase by Solvay Enzymes those.Press composition weight meter, can proteolytic enzyme be joined in the composition of the present invention with the amount of 0.0001-4% organized enzyme.
Preferred amylase comprises: for example, from the α-Dian Fenmei that the special bacterial strain of licheniformin (B licheniformis) obtains, it has more detailed narration in GB1269839.The amylase that preferred commerce is buied comprises: for example those that sell with trade name Rapidase by Gist-Brocades and sell with trade name Termamy and BAN by Novo Industries A/S those.Press composition weight meter, the amount of amylase with the 0.0001-2% organized enzyme can be joined in the composition of the present invention.
Press composition weight meter, the amount that lipolytic enzyme exists can be 0.0001-2%, preferred 0.001-1%, the most preferably active lipolytic enzyme of 0.001-0.5%.
This lipase can be mould or bacterial origin, and for example it is to comprise that from detritus enzyme genus, tea toadstool genus or the Rhodopseudomonas that produces lipase the bacterial strain of Pseudomonas pseudoalcaligenes and Pseudomonas fluorescens (Pseudomas fluorescens) obtains.From the chemistry of these bacterial strains or the lipase of gene modification also is useful in this article.Preferred lipase is from the Pseudomonaspseudoalcaligenes deutero-, and it is described among the European patent EP-B-0218272 that has authorized.
The preferred lipase of herein another is to obtain by expressing this gene from Humicola lanuginosa clone gene and as host's aspergillus oryzae, as described in European patent application EP-A-0258068, it can be from Novo Industri A/S, Bagsvaerd, Denmark obtains with trade name Lipolase.This lipase also has description in the US4810414 of promulgation on March 7th, 1989.
Organic polyhydroxyl compound
Organic polyhydroxyl compound is the preferred annexing ingredient of detergent composition of the present invention, and preferably as the component existence of any grain fraction, they can play a part for example grain fraction to be bonded together in grain fraction.Basically refer to any organic polyhydroxyl compound that in detergent composition, is used as dispersion agent, antiredeposition and soil-suspending agent usually herein about organic polyhydroxyl compound, comprise any high-molecular weight organic polyhydroxyl compound of describing as the clay flocculating agent herein.
Press composition weight meter, organic polyhydroxyl compound is generally with 0.1-30%, preferred 0.5-15%, and most preferably the content of 1-10% joins in the composition of the present invention.
The example of organic polyhydroxyl compound comprises poly carboxylic acid or its salt of water miscible organic homopolymerization or copolymerization, and wherein this poly carboxylic acid comprises at least 2 each other by no more than 2 carboxyls that carbon atom is separated.The polymkeric substance of back one type is disclosed among the GB-A-1596756.The example of salt is the multipolymer of the polyacrylate of MWt 2000-5000 and itself and maleic anhydride like this, and the molecular weight of such multipolymer is 20000-100000, especially 40000-80000.
The polyamino compound is useful in this article, and it comprises from aspartate-derived those, for example those disclosed in EP-A305282, EP-A-305283 and EP-A-351629.
Those that contain the ter-polymers, the especially molecular-weight average that are selected from toxilic acid, vinylformic acid, poly aspartic acid and vinyl alcohol monomeric unit and be 5000-10000 also are applicable to herein.
Other organic polyhydroxyl compound that is suitable for joining in this paper detergent composition comprises derivatived cellulose for example methylcellulose gum, carboxymethyl cellulose, HYDROXY PROPYL METHYLCELLULOSE and Natvosol.
Other useful organic polyhydroxyl compound is a polyoxyethylene glycol, and particularly molecular weight is 1000-10000, more especially 2000-8000, most preferably from about those of 4000.
Suds suppressor
Detergent composition of the present invention preferably contains suds suppressor when it being mixed with when being used to machine-wash composition, and the amount of its existence is the 0.01-15% of composition weight, preferred 0.05-10%, most preferably 0.1-5%.
The suitable suds suppressor that is used for herein consists essentially of any known anti-foam compound, comprising: for example anti-foam compound of siloxanes and 2-alkyl alcohol are prevented the foam compound.
About anti-foam compound, referred to herein such as suppressing by detergent composition solution any compound of foaming that produces when particularly stirring this solution or forming process or the mixture of compound.
The particularly preferred alveolation compound that presses down that is used for herein is the anti-foam compound of siloxanes, is defined as any anti-foam compound that comprises the siloxanes component herein.The anti-foam compound of such siloxanes generally also contains the silicon-dioxide component.As employed usually in this paper and the whole industry, term " siloxanes " comprises the various relative high molecular weight polymers that contains siloxane unit and all kinds alkyl.The anti-foam compound of preferred siloxanes is a siloxanes, particularly has the polydimethylsiloxane of trimethylsilyl end groups block unit.
Other suitable anti-foam compound comprises mono carboxylic lipid acid and its water-soluble salt.These materials have description in the US2954347 of the Wayne St.John of promulgation on September 27 nineteen sixty.This mono carboxylic lipid acid and its salt as suds suppressor generally have 10-24 carbon atom, the hydrocarbyl chain of preferred 12-18 carbon atom.Suitable salt comprises basic metal for example sodium, potassium and lithium salts and ammonium and alkanol ammonium salts.
Other suitable anti-foam compound comprises: for example, and high molecular fatty ester (for example fatty acid glyceryl ester), the fatty acid ester of monovalent alcohol, aliphatics C
18-C
40The alkylating aminotriazine of ketone (for example stearone) N-for example three-to six-alkyl melamine or as cyanuryl chloride and 2 or 3 moles contain that the product of the uncle of 1-24 carbon atom or secondary amine, propylene oxide, two stearic amide and single stearyl-two basic metal (for example sodium, potassium, lithium) phosphoric acid salt and phosphoric acid ester forms two-to four-alkyl diamine chloro triazine.
The preferred foam system that presses down comprises:
(a) anti-foam compound, the anti-foam compound of preferred siloxanes most preferably is the anti-foam compound of siloxanes that comprises following mixture:
(i) in the weight of the anti-foam compound of this siloxanes, content is 50-99%, the polydimethylsiloxane of preferred 75-95%; With
(ii) in the weight of the anti-foam compound of this siloxanes/silicon-dioxide, content is 1-50%, the silicon-dioxide of preferred 5-25%;
Wherein with 5-50% (weight), the amount of preferred 10-40% (weight) adds the anti-foam compound of described silica/silicon oxygen alkane;
(b) compound dispersing agent, most preferably comprise silicone glycols rake multipolymer, its polyoxyalkylene content is 72-78% (weight) and oxyethane and the ratio of propylene oxide is 1: 0.9-1: 1 (weight), and its amount is 0.5-10% (weight), preferred 1-10% (weight); Particularly preferred this class silicone glycols rake multipolymer is DCO544, can obtain with trade(brand)name DCO544 from DOW Corning;
(c) inert support fluid compound comprises that most preferably ethoxylation degree is 5-50, the C of preferred 8-15
16-C
18Ethoxylated alcohol, its amount is 5-80% (weight), preferred 10-70% (weight);
Granular suds suppressing system very preferably is described among the EP-A-0210731 and comprises that anti-foam compound of siloxanes and fusing point are 50-85 ℃ organic carrier, and wherein this organic carrier comprises glycerine and the monoesters with the lipid acid that contains 12-20 carbon atom alkyl chain.EP-A-0210721 discloses other preferred granular suds suppressing system, and wherein this organic carrier is to have lipid acid or the alcohol that contains 12-20 carbon atom, or its mixture, and its fusing point is 45-80 ℃.
The soft system of clay
Detergent composition can contain the soft system of clay, and it comprises clay mineral compound and optional clay flocculating agent.
This clay mineral compound is the smectic clays compound preferably.Smectic clays is disclosed in United States Patent (USP) 3862058,3948790,3954632 and 4062647.European patent EP-the A-299575 of Procter and GambleCompany and EP-A-313146 have described suitable organic polymer clay flocculating agent.
The polymeric dye transfer inhibitor
Detergent composition herein also can contain 0.01-10% (weight), the polymeric dye transfer inhibitor of preferred 0.05-0.5% (weight).
This polymeric dye transfer inhibitor is preferably from the polyamine N-oxide polymkeric substance, the multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole, polyvinylpyrrolidonepolymers polymers, or its mixture.
A) polyamine N-oxide pllymers
Be applicable to that herein polyamine N-oxide pllymers contains the unit of following structural formula:
Wherein P be polymerizable unit and
A is
-O-,-S-,-N-; X is 0 or 1;
R is aliphatic series, aromatic series, heterocycle or alicyclic group or its mixture of aliphatic series, ethoxylation, the part that the nitrogen-atoms of N-O group can be connected thereto or wherein the nitrogen of N-O group is these groups.
The N-O group can be represented by following general formula:
Or
R wherein
1, R
2, R
3Be aliphatic series, aromatic series, heterocycle or alicyclic group or its mixture, x or/and y or/and z is 0 or 1, wherein the nitrogen-atoms of N-O group can be connected or form the part of arbitrary above-mentioned group.This N-O group can be that the part of this polymerizable unit (P) maybe can be connected on this polymeric skeleton, perhaps can be the two.
The polyamine N-oxide that suitable wherein N-O group forms a polymerizable unit part comprises that R wherein is selected from the polyamine N-oxide of aliphatic series, aromatic series, alicyclic ring or heterocyclic group.The described polyamine N-oxide of one class comprises the wherein polyamine N-oxide of the nitrogen-atoms formation R group part of N-O group.Preferred polyamine N-oxide compound is that wherein R is for example those of pyridine, pyrroles, imidazoles, pyrroline, piperidines, quinoline, acridine and its derivative of heterocyclic group.
Other suitable polyamine N-oxide is that wherein the N-O group is connected to polyamine N-oxide on the polymerizable unit.Preferred this class polyamine N-oxide comprises that wherein R is the polyamine N-oxide of the general formula (I) of aromatic series, heterocycle or alicyclic group (wherein the nitrogen-atoms of N-O functional group is a described R group part).This class examples of substances is that wherein R is for example polyamine oxide compound of pyridine, pyrroles, imidazoles and its derivative of heterogeneous ring compound.
Can obtain the polyamine oxide compound with almost any polymerization degree.The polymerization degree is not crucial, as long as this material has needed water-soluble and dye suspension ability.Usually, molecular-weight average is in the scope of 500-1000000.
B) its polymers of N-vinyl pyrrolidone and N-vinyl imidazole
Be suitable for herein be N-vinyl imidazole and N-vinylpyrrolidone copolymers, its molecular-weight average is in the scope of 5000-50000.The N-vinyl imidazole of preferred this multipolymer and the mol ratio of N-vinyl pyrrolidone are 1-0.2.
C) Polyvinylpyrolidone (PVP)
The present composition also can use the Polyvinylpyrolidone (PVP) (" PVP ") of molecular-weight average as 2500-400000.Suitable Polyvinylpyrolidone (PVP) is from ISP Corporation, NewYork, NY and Montreal, Canada buys with ProductName PVP K-15 (viscosity molecular weight is 10000), PVP K-30 (molecular-weight average is 40000), PVP K-60 (molecular-weight average is 160000) and PVP K-90 (molecular-weight average is 360000).Also can obtain PVP K-15 from ISP Corporation.Can comprise Sokalan HP 165 and Sokalan HP 12 from other suitable Polyvinylpyrolidone (PVP) that BASF Cooperation buys.
D) Ju Yi Xi oxazolidinone
Detergent composition herein also can use Ju Yi Xi oxazolidinone as the polymeric dye transfer inhibitor.The molecular-weight average of described Ju Yi Xi oxazolidinone is 2500-400000.
E) polyvinyl imidazol
Detergent composition herein also can use polyvinyl imidazol as the polymeric dye transfer inhibitor.The molecular-weight average of described polyvinyl imidazol is preferably 2500-400000.
White dyes
Detergent composition herein also randomly contains the specific type hydrophilic white dyes of the 0.005-5% that has an appointment (weight).
Useful herein hydrophilic white dyes comprises those with following structural formula:
R wherein
1Be selected from anilino, N-2-two-hydroxyethyl and NH-2-hydroxyethyl; R
2Be selected from N-2-pair-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morpholino, chlorine and amino; With M be for example sodium or potassium of the salifiable positively charged ion of shape.
As the R in following formula
1Be anilino, R
2Be N-2-two-hydroxyethyl and M are positively charged ions for example during sodium, this whitening agent is 4,4 ' ,-two [(4-anilino-6-(N-2-two-hydroxyethyl)-s-triazine-2-yl) amino]-2,2 '-stilbene disulfonic acid and disodium salt.This specific whitening agent is sold by Ciba-Geigy Corporation with trade(brand)name Tinopal-UNPA-GX.Tinopal-UNPA-GX is preferred hydrophilic white dyes useful in this paper detergent composition.
As the R in following formula
1Be anilino, R
2Be that N-2-hydroxyethyl-N-2-methylamino and M are positively charged ions for example during sodium, this whitening agent is 4,4 '-two [(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl) amino]-2,2 '-stilbene disulfonic acid disodium salt.This specific whitening agent is sold by Ciba-Geigy Corporation with trade(brand)name Tinopal-5BM-GX.
As the R in following formula
1Be anilino, R
2Be that morpholino and M are positively charged ions for example during sodium, this whitening agent is 4,4 '-two [(4-anilino-6-morpholino-s-triazine-2-yl) amino] 2,2 '-stilbene disulfonic acid, sodium salt.This specific whitening agent is sold by Ciba-GeigyCorporation with trade(brand)name Tinopal-AMS-GX.
Cationic fabric softener
Cationic fabric softener can be joined in the composition of the present invention.Suitable cationic fabric softener is included in disclosed water-soluble tertiary amine or two long-chain acid amides materials among GB-A-1514276 and the EP-B-0011340.
Generally with 0.5-15% (weight), the total amount of 1-5% (weight) adds cationic fabric softener usually.
Other optional components
Other optional components that is suitable for being included in the present composition comprises spices, and colorant and filling salt, sodium sulfate are preferred filling salts.
The pH of composition
The present composition preferably is at least 10.0 as the pH of 1% distilled water solution, more preferably 10.0-12.5, most preferably 10.5-12.0.
The form of composition
Composition of the present invention can adopt various physical form, comprises granular, sheet, strip and liquid form.Especially, said composition is so-called spissated granular detergent composition, and it is adapted to pass through distribution device and joins in the washing machine, and this distribution device is placed in the washing machine rotary drum with dirty fabric.
Median size according to the basic composition of granular composition of the present invention should be preferably such, and it makes and be not more than 5% particle diameter greater than 1.7mm, is not more than 5% particle diameter less than 0.15mm.
Defined herein term median size is calculated by composition is divided into a lot of particle size fractions (generally being 5 particle size fractions) at a series of Tyler sieve top sieves.The weight particle size fraction that obtains thus is to the aperture mapping of sieve.Median size is that sample passes through the aperture of 50% (weight).
The bulk density of granular detergent composition of the present invention generally is the bulk density of 600g/l, more preferably 650-1200g/l at least.Bulk density is by being measured by simple funnel and measuring cup device, and it is installed in by rigidity that coniform funnel on the base is formed and a plate valve is housed so that allow object in the funnel be emptied to be placed in the axially aligned coniform measuring cup below the funnel in its lower end.This funnel 130mm height, the upper and lower ends internal diameter is respectively 130mm and 40mm.It is to install like this, makes lower end 140mm on base.The height overall of measuring cup is 90mm, and internal diameter is 87mm, and external diameter is 84mm.It demarcates volume is 500ml.
In order to measure, topple over hand this funnel is filled up powder, drive plate valve greatly and allow the powder measuring cup that overfills.From base, take out this measuring cup that fills up and with a straight flange instrument for example scraper remove excessive powder by its upper limb.This measuring cup that fills up of weighing multiply by 2 values that obtain by powder weight bulk density (g/l) is provided.If desired, repeat to measure.
Said composition preferably is dissolved in cold water or the cold water, and promptly the easy dissolution of composition is about 0-32.2 ℃ in temperature, in preferred 1.6-10 ℃ the water.
The surfactant agglomerates particle
Surfactant system herein preferably is present in the granular composition with surfactant agglomerates particulate form, and it can take sheet, bead, ball, slice, belt-like form, but preferably takes granular form.This particulate method of most preferred processing is by being controlled in the specific restriction with powder (for example silico-aluminate, carbonate) and the agglomeration of highly active tensio-active agent cream and with the particle diameter of the agglomerate that obtains.Such method comprises that the powder with significant quantity mixes in one or more agglomeration machines with highly active tensio-active agent cream, the agglomeration machine is: for example, disc type agglomeration machine, Z-type blade mixing machine, or more preferably the tandem mixing machine for example make by Schugi (Holland) BV those, 29 Chroomstraat, 8211 AS, Lelystad, Netherland, with GebruderLodige Maschinenbau GmbH, D-4790 Paderborn 1, Elsenerstrasse 7-9, Postfach 2050, Germany.The most preferred high shear mixer that is to use, for example LodigeCB (trade name).
Highly active tensio-active agent cream contains and is generally 50-95% (weight), the mixture of the tensio-active agent of preferred 70-85% (weight) and suitable acid source.But can under the low temperature of the anion surfactant degraded that is enough to keep the high temperature of pumping viscosity but is enough to avoid used, this ointment pumping be advanced in the agglomeration machine.The service temperature of this lotion generally is 50-80 ℃.
In particularly preferred embodiment of the present invention, detergent composition has greater than the density of about 600g/l and is to contain greater than about 5% (weight) alkali source, the powder or the particle form of preferred carbonic acid (hydrogen) salt or percarbonate.This carbonate be do to add or provide by the agglomeration machine.
The laundry washing methods
Machine washing clothes washing method herein is included in the washing machine with dissolving or is dispersed in the machine-wash aqueous solution of laundry detergent composition of wherein the present invention of significant quantity handles the dirt clothes.About the detergent composition of significant quantity, it refers to the product dissolving of 40-300g or is dispersed in the washing soln of 5-65 liter, and this is normally used common product dosage and a washing soln volume in the machine washing clothes washing method of routine.
Aspect preferred use, in washing methods, use distribution device.This distribution device has been full of Betengent product, and with it product is introduced directly into before cycles of washing begins in the rotating cylinder of washing machine.Its volume capacity should be such so that can contain enough conducts common Betengent product that uses in this washing methods.
In case the washing machine load has clothes, the distribution device that contains Betengent product just is put in the rotating cylinder.When the cycles of washing of washing machine began, water was introduced in this rotating cylinder and rotating cylinder rotates periodically.The design of this distribution device should be such, causes it can contain dried Betengent product, then during cycles of washing along with its stirring (because rotating cylinder rotation, also as the result who contact with washing water) makes this product release.
For the ease of discharge Betengent product during washing, this device can have a lot of perforates, and Betengent product can pass through these holes.In addition, this device can be by liquid permeable but not the material of porous solid phase prod make, this can discharge the dissolved product.Preferably, this Betengent product when cycles of washing begins just rapidly dissolving so that the product of temporary transient high local concentrations is provided in this cycles of washing stage rotating cylinder at washing machine.
Preferred distribution device can re-use, and is the integrity that promptly all keeps container in dried state and during the cycles of washing that designs by this way.Narrated the particularly preferred distribution device that is used for the present composition below in the patent: GB-B-2157717, GB-B-2157718, EP-A-0201376, EP-A-0288345 and EP-A-0288346.Also described the particularly preferred device that is used for the granular laundry product by J.Bland at the disclosed goods of 41-46 page or leaf of the Manufacturing Chemist in November, 1989, it is to be referred to as " granulette " type usually.Another is disclosed among the PCT patent application WO94/11562 with the preferred distribution device that detergent composition herein uses.
Particularly preferred distribution device is disclosed in european patent application 0343069 and 0343070.The device that back one application discloses the flexible cover that comprises the bag form that extends from the support ring that limits the aperture adopts this aperture so that allow this bag to be useful on once washing round-robin adequate prod in the washing process.The part washing medium flows in this bag by this aperture, dissolves this product, and solution outwards flows out by this aperture and enters in the washing medium then.This support ring is equipped with shielding unit and flows out outward with the not dissolved product that prevents to wet, and this device generally comprises the wall extension or the similar structure of extending from the center hub the spoke wheel configuration, and wherein this wall has the helical form.
In addition, this distribution device can be flexible container, for example bag or box.This bag can be so that maintenance thing wherein is for example disclosed in european patent application 0018678 with the filamentary structure of water impervious protective material coating.In addition, it can be formed by the insoluble synthetic polymeric material of water, and this material is designed to disruptive edge sealer or closure in water-bearing media, as disclosed in european patent application 0011500,0011501,0011502 and 0011968.Make things convenient for the frangible closure of water of form to comprise water-soluble binder, it is for example placed or with its sealing on a limit of the bag that forms of polyethylene or polypropylene along water impervious polymeric membrane.
The packing of composition
The commercial embodiments of this bleaching composition may be packaged in any suitable containers, comprises those containers that constitute from paper, cardboard, plastic material and any proper lamination thing.Preferred packing embodiment is described in the european patent application 94921505.7.
Be used for the abbreviation of following embodiment
In detergent composition, abbreviation component symbol has following meaning:
LAS: straight chain C
12Sodium alkyl benzene sulfonate
TAS: tallow alkyl sodium sulfate
C45AS: C
14-C
15Straight-chain alkyl sulfate
CXYEZS: with the C of Z moles of ethylene oxide condensation
1X-C
1YBranched-chain alkyl sulfuric acid
Sodium C45E7: with the C that is mainly of average 7 moles of ethylene oxide condensations
14-C
15
Straight chain primary alcohol C25E3: with the C that is mainly of average 3 moles of ethylene oxide condensations
12-C
15
Branched-chain primary alcohol C25E5: with the C that is mainly of average 5 moles of ethylene oxide condensations
12-C
15
Branched-chain primary alcohol CEQ: R
1COOCH
2CH
2N
+(CH
3)
3, R
1=C
11-C
13QAS: R
2N
+(CH
3)
2(C
2H
4OH), R
2=C
12-C
14Soap: the straight-chain alkyl carboxylic acid who obtains from 80/20 tallow and coconut oil blend
Sodium TFAA: C
16-C
18Alkyl N-methyl glucose amide TPKFA: C
12-C
14The full fraction lipid acid STPP of topping: anhydrous sodium tripolyphosphate zeolite A: formula Na
12(AlO
2SiO
2)
12.27H
2The primary particle diameter of O is 0.1-10
The hydrated sodium aluminosilicate NaSKS-6 of micron: formula δ-Na
2Si
2O
5The crystalline layered silicate citric acid: Citric Acid, usp, Anhydrous Powder carbonate: particle diameter is the anhydrous sodium carbonate supercarbonate of 200-900 μ m: particle diameter is the anhydrous sodium bicarbonate silicate of 400-1200 μ m: amorphous silicic sodium (SiO
2: Na
2O=2.0) sodium sulfate: anhydrous slufuric acid na citrate: activity is the lemon of 86.4% size distribution at 425-850 μ m
Acid trisodium dihydrate MA/AA: toxilic acid/acrylic copolymer of 1: 4, molecular-weight average are approximately
70000CMC: Xylo-Mucine proteolytic enzyme: sell with trade(brand)name Savinase by NOVO Industries A/S
Decomposition of protein enzyme (activity is 4KNPU/g) Alcalase: by the decomposition of protein enzyme (activity of NOVO Industries A/S sale
Be 3AU/g) cellulase: sell with trade(brand)name Carezyme by NOVO IndustriesA/S
Cellulase (activity is 1000CEVU/g) amylase: sell with trade(brand)name Termamyl 60T by NOVO Industries A/S
The amylolytic enzyme of selling (the active 60KUN/g of being) lipase: sell with trade(brand)name Lipolase by NOVO Industries A/S
Lipolytic enzyme (activity is 100KLU/g) Endolase: sell the Endoglunase enzyme by NOVO Industries A/S and (live
Property is 3000CEVU/g) PB4: sodium perborate tetrahydrate, chemical formula are NaBO
2.3H
2O.H
2O
2PB1: anhydrous sodium perborate monohydrate, chemical formula are NaBO
2.H
2O
2Percarbonate: chemical formula is 2Na
2CO
3.3H
2O
2SPC-D NOBS: the nonanoly acyloxy benzene sulfonate TAED of sodium-salt form: tetra acetyl ethylene diamine DTPMP: the two inferior second of selling with trade name Dequest 2060 by Monsanto
Base the floating of triamine five (methylene phosphonic acid salt) photoactivation: be encapsulated in the white agent whitening agent of sulfonation zinc phthalocyanine phthalocyanine 1: 4 in the soluble bleaching cyclodextrin poly compound, 4 '-two (2-sulfo group styryl) biphenyl sodium whitening agent 2: 4,4 '-two [(4-anilinos-6-morpholino-1,3,5-triazine-2-yl) ammonia
Base] 2; 2 '-stilbene sodium disulfonate HEDP: 1,1-hydroxyl ethane di 2 ethylhexyl phosphonic acid PVNO: polyvinyl pyridine N-oxide PVPVI: the multipolymer SRP1 of polyvinylpyrrolidone and vinyl imidazole: sulfo group benzene first with oxyethylene group oxygen base and terephthaloyl skeleton
The end capped ester SRP2 of acyl group: poly-(1,2 propylidene terephthalate) of diethoxyization is short, and block is poly-
The compound polysiloxane is anti-: with polydimethyl foam agent silicone foam control agent, described Foam Control and the described dispersion agent of siloxanes-oxyalkylene copolymers as dispersion agent
Ratio be 10: 1-100: 1 alkali source: the NaOH of % weight equivalent, it is to use described alkali herein
The release test method obtains
Among the embodiment, all content are all represented with the % of composition weight below.
The present invention is used in particular for the detergent formulation that does not contain SYNTHETIC OPTICAL WHITNER of washing colored fabric below embodiment 1 preparation:
| A | B | |
| The powder of ejection | ||
| Zeolite A | 15.0 | - |
| Sodium sulfate | - | - |
| Citrate trianion | 10.0 | 8.0 |
| LAS | 3.0 | - |
| CEQ | 2.0 | 1.3 |
| DTPMP | 0.4 | - |
| CMC | 0.4 | - |
| MA/AA | 4.0 | - |
| Agglomerate | ||
| C45AS | - | 11.0 |
| LAS | 6.0 | - |
| TAS | 3.0 | - |
| Silicate | 4.0 | - |
| Zeolite A | 10.0 | 13.0 |
| CMC | - | 0.5 |
| MA/AA | - | 2.0 |
| Citric acid | 4.0 | 3.0 |
| Carbonate | 9.0 | 7.0 |
| The spraying composition | ||
| Spices | 0.3 | 0.5 |
| C45E7 | 4.0 | 4.0 |
| C25E3 | 2.0 | 2.0 |
| The additive of doing | ||
| MA/AA | - | 3.0 |
| N aSK-6 | - | ?12.0 |
| Supercarbonate | 7.0 | ?5.0 |
| Carbonate | 8.0 | ?7.0 |
| PVPVI/PVNO | 0.5 | ?0.5 |
| Alcalase | 0.5 | ?0.9 |
| Lipase | 0.4 | ?0.4 |
| Amylase | 0.6 | ?0.6 |
| Cellulase | 0.6 | ?0.6 |
| The polysiloxane antifoams | 5.0 | ?5.0 |
| The additive of doing | ||
| Sodium sulfate | 0.0 | ?0.0 |
| Its excess (water and other component) | 100.0 | ?100.0 |
| Density (g/l) | 700 | ?700 |
The high density detergent agent prescription that contains SYNTHETIC OPTICAL WHITNER of the present invention below embodiment 2 preparations:
| ?C | ?D | |
| The powder of ejection | ||
| Zeolite A | ?15.0 | ?15.0 |
| Sodium sulfate | ?0.0 | ?0.0 |
| LAS | ?3.0 | ?3.0 |
| QAS | ?- | ?1.5 |
| CEQ | ?2.0 | ?- |
| DTPMP | ?0.4 | ?0.4 |
| CMC | ?0.4 | ?0.4 |
| MA/AA | ?4.0 | ?2.0 |
| Agglomerate | ||
| LAS | ?4.0 | ?4.0 |
| TAS | ?2.0 | ?1.0 |
| Silicate | ?3.0 | ?4.0 |
| Citric acid | 2.0 | ?3.0 |
| Zeolite A | 8.0 | ?8.0 |
| Carbonate | 8.0 | ?6.0 |
| The spraying composition | ||
| Spices | 0.3 | ?0.3 |
| C45E7 | 2.0 | ?2.0 |
| C25E3 | 2.0 | ?- |
| The additive of doing | ||
| Citrate trianion | 5.0 | ?2.0 |
| Supercarbonate | - | ?- |
| Carbonate | 8.0 | ?10.0 |
| TEAD | 6.0 | ?5.0 |
| PB1 | 14.0 | ?10.0 |
| The polyethylene oxide of MW5000000 | - | ?0.2 |
| POLARGEL NF | - | ?10.0 |
| Proteolytic enzyme | 1.0 | ?1.0 |
| Lipase | 0.4 | ?0.4 |
| Amylase | 0.6 | ?0.6 |
| Cellulase | 0.6 | ?0.6 |
| The polysiloxane antifoams | 5.0 | ?5.0 |
| The additive of doing | ||
| Sodium sulfate | 0.0 | ?0.0 |
| Its excess (water and other component) | 100.0 | ?100.0 |
| Density (g/l) | 850 | ?850 |
Embodiment 3
High density detergent agent prescription of the present invention below the preparation:
| E | ?F | |
| Agglomerate | ||
| C45AS | 11.0 | ?14.0 |
| CEQ | - | ?3.5 |
| Zeolite A | 15.0 | ?6.0 |
| Citric acid | 1.5 | ?2.0 |
| Carbonate | 4.0 | ?8.0 |
| MA/AA | 4.0 | ?2.0 |
| CMC | 0.5 | ?0.5 |
| DTPMP | 0.4 | ?0.4 |
| The spraying composition | ||
| C25E5 | 5.0 | ?5.0 |
| Spices | 0.5 | ?0.5 |
| The additive of doing | ||
| HEDP | 0.5 | ?0.3 |
| SKS6 | 13.0 | ?10.0 |
| Citrate trianion | 3.0 | ?1.0 |
| TAED | 5.0 | ?7.0 |
| Percarbonate | 20.0 | ?20.0 |
| SRP1 | 0.3 | ?0.3 |
| Proteolytic enzyme | 1.4 | ?1.4 |
| Lipase | 0.4 | ?0.4 |
| Cellulase | 0.6 | ?0.6 |
| Amylase | 0.6 | ?0.6 |
| The polysiloxane antifoams | 5.0 | ?5.0 |
| Whitening agent 1 | 0.2 | ?0.2 |
| Whitening agent 2 | 0.2 | ?- |
| Its excess (water and other component) | 100 | ?100 |
| Density (g/l) | 850 | ?850 |
Claims (11)
1. preparing washing agent method for compositions comprises:
I) thus cleaning composition tensio-active agent and acid source form the surfactant/acid mixture; With
Ii) form agglomerant surfactant/acid mixture.
2. make this agglomerant surfactant/acid mixture forming particle, sheet, bead, ball, slice or band shape according to the process of claim 1 wherein.
3. according to the process of claim 1 wherein that this agglomerant surfactant/acid mixture is pressed into sheet.
4. according to the method for above-mentioned arbitrary claim, wherein step (i) also comprises alkali source is mixed with detergent surfactant and acid source.
5. according to arbitrary method of claim 1-3, wherein (iii) alkali source is joined in the agglomerant surfactant/acid mixture as the component of separating.
6. according to the method for claim 4 or 5, wherein this alkali source comprises the basic salt that is selected from basic metal or alkaline earth metal carbonate, supercarbonate, sesquicarbonate or alkali metal percarbonate.
7. according to the method for above-mentioned arbitrary claim, wherein this detergent surfactant is negatively charged ion, nonionic, positively charged ion, amphoterics, or its mixture.
8. according to the method for above-mentioned arbitrary claim, wherein this acid source comprises organic acid, mineral or mineral acid.
9. method according to Claim 8, wherein this acid source is citric acid, pentanedioic acid, succsinic acid, hexanodioic acid, mono phosphoric acid ester sodium, sodium pyrosulfate or boric acid.
10. according to the detergent composition of the method for above-mentioned arbitrary claim preparation.
11. method of washing clothes in the family expenses washing machine, this method comprise that the detergent composition with the claim 10 of significant quantity joins in the distribution device that is placed in the washing machine turning barrel, the distribution that perhaps joins washing machine is drawn in the box.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9616113A GB2315763A (en) | 1996-07-31 | 1996-07-31 | Preparation of an agglomerated detergent composition comprising a surfactant a an acid source |
| GB9616113.8 | 1996-07-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1230983A true CN1230983A (en) | 1999-10-06 |
Family
ID=10797812
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 97198105 Pending CN1230983A (en) | 1996-07-31 | 1997-07-23 | Detergent composition and its preparation |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0915960A4 (en) |
| CN (1) | CN1230983A (en) |
| AR (1) | AR008117A1 (en) |
| BR (1) | BR9710898A (en) |
| CA (1) | CA2261948C (en) |
| GB (1) | GB2315763A (en) |
| WO (1) | WO1998004672A1 (en) |
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| US6262004B1 (en) * | 1999-11-10 | 2001-07-17 | Eco-Safe, L.L.C. | Cleaning composition for autonomous cleaning system |
| US7053040B2 (en) | 1999-11-10 | 2006-05-30 | Eco-Safe Technologies, L.L.C. | Autonomous cleaning composition and method |
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| WO2008040151A1 (en) * | 2006-09-01 | 2008-04-10 | Tao Wang | Synthetic detergent and its preparation method |
| MX2013001062A (en) | 2010-07-27 | 2013-02-21 | Unilever Nv | Detergent composition. |
| US11359168B2 (en) | 2020-04-03 | 2022-06-14 | One Home Brands, Inc. | Stable anhydrous laundry detergent concentrate and method of making same |
| CA3160403A1 (en) * | 2020-04-03 | 2021-10-07 | Syed Humza Naqvi | Stable anhydrous laundry detergent concentrate and method of making same |
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| ES2109858B1 (en) * | 1994-11-23 | 1998-08-16 | Menarini Lab | NEW ACID DERIVATIVES (+) - (S) -2- (3-BENZOILFENIL) PROPIONICO WITH ANALGESIC ACTION AND PROCEDURE FOR ITS OBTAINING. |
| EP0753571A1 (en) * | 1995-07-10 | 1997-01-15 | The Procter & Gamble Company | Process for making granular detergent composition |
| AU1069697A (en) * | 1995-12-28 | 1997-07-28 | Rhone-Poulenc Surfactants And Specialties, L.P. | Processes for producing solid surfactant compositions with decreased dissolution rates |
| WO1997024423A1 (en) * | 1995-12-28 | 1997-07-10 | Rhone-Poulenc Surfactants & Specialties, L.P. | Processes for producing solid surfactant compositions with enhanced dissolution rates |
| ATE223472T1 (en) * | 1996-03-15 | 2002-09-15 | Amway Corp | METHOD FOR PRODUCING A FREE-FLOWING AGGLOMERISED DETERGENT CONTAINING NIOSUTENSIDS |
-
1996
- 1996-07-31 GB GB9616113A patent/GB2315763A/en not_active Withdrawn
-
1997
- 1997-07-23 CA CA002261948A patent/CA2261948C/en not_active Expired - Fee Related
- 1997-07-23 WO PCT/US1997/012965 patent/WO1998004672A1/en not_active Application Discontinuation
- 1997-07-23 EP EP97936189A patent/EP0915960A4/en not_active Withdrawn
- 1997-07-23 BR BR9710898-7A patent/BR9710898A/en unknown
- 1997-07-23 CN CN 97198105 patent/CN1230983A/en active Pending
- 1997-07-30 AR ARP970103447A patent/AR008117A1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EP0915960A1 (en) | 1999-05-19 |
| BR9710898A (en) | 2000-10-24 |
| GB9616113D0 (en) | 1996-09-11 |
| CA2261948A1 (en) | 1998-02-05 |
| WO1998004672A1 (en) | 1998-02-05 |
| GB2315763A (en) | 1998-02-11 |
| CA2261948C (en) | 2002-10-15 |
| EP0915960A4 (en) | 2001-09-19 |
| AR008117A1 (en) | 1999-12-09 |
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| SE01 | Entry into force of request for substantive examination | ||
| AD01 | Patent right deemed abandoned | ||
| C20 | Patent right or utility model deemed to be abandoned or is abandoned |